Manufacture of vat dyestuffs of the isodibenzanthrone series



Patented Mar. 19, 1929 UNITED STATESPATENT OFFICE.

ALOIS ZINKE, F GRAZ, AUSTRIA, ASSIGNOR TOFELI CE IBENSA, OF GENOA, ITALY.-

v MANUFACTURE OF VAT DYESTUFFS OF THE ISODIBENZANTHRONE SERIES. No Drawing. Application filed September 30, 1925, Serial No. 59,722, and in Austria November 11, 1924.

My invention relates to the manufacture of stuffs are obtained by treating the dibenzoyl '50 vat dye stufi's of the isodibenzanthrone series dibromo perylene with melting alkalies. from diaroyl dihalogen perylenes having two halogen groups in the perylene nucleus and Example each aroyl group occupying a p P 3 parts by weight of dibenzoyl dichloroto one of the/ halog n gr p and h g a perylene satisfying the above conditions are f Q POSltlOIL $11911 y dlhalogen heated to boiling with 15 parts of powdered perylenes may be Obt m y condensmg caustic alkali and. 60 parts by volume ,of Sultable stalftlng matenflls y mefms of y' quinoline for 3 to 4 hours. The dye stuff thus dr alummmm o q that 1s to y, y formed is filtered 0a and washed with alcohol the known method of Fnedel-Crafts. d t Th t t amounts t 7 60 y mYentlon conslsts 1n trfiatlng h d Impurities. if there are any, may be removed d1aroyl d1halogen perylenes wlth alkal metal b means if l i l ti cid Th dib hydroxlcl 11 1 PTBSBIIQQ f organ10 zoyl dibromo or dichloro perylene above re- 15 vents such as anll ne 1 qu ferred to may be obtained by condensing 3,9 Example L dlbromo 0r dichloro perylene with benzoyl 1 chlor de by means of anhydrous aluminium r p by e g 0f dlbenzoyl dlbromp chloride. The following are the formula il- R y satlsfylng ab9ve named q r lustrating the reaction described in Example tlons and prepared as hereinafter described, 1 E l 2 i ill st ted b i il f is heated with 50 Parts y weight of aniline mulae in which, however, chlorine atoms in- 70,

of potassium for an hour to slow boiling. v The liquid becomes brownish green in color, a non 1n ;the perylene nuclei violet precipitate being deposited therefrom.

After one hours boiling the precipitate is I p 75 and 5 parts by weight of powdered hydroxide Stead of bromine atoms occupy the 3,9 POSL separated by filtration and washed with alcohol and water, the product then forming a dark powder which when heated with dilute aqueous sodium hydroxide gives a blue vat showing red fluorescence. Cotton on tak- 8O ing up the vat becomes blue and in contact with air it becomes violet. The color is very fast and more particularly fast against the action of chlorine, acids and alkalies, and is also fast as to washing. In concentrated sulphuric acid the dye stufl' dissolves with a blue. green color and shows red fluorescence. On diluting with water the dye stufi is precipi- 40 tated'in violet, flakes. In solvents having. a low boiling point such as alcohol, acetone, ether, chloroform, bisulphide of carbon, benzene, etc, the dye stuff is almost insoluble; 3,9-dich1oro- 3,9 dichloro-4J0-diben- Dyestu'fl in boiling nitrobenzeneit dissolves slightly Wynne mylpemen more easil with a blue color and red fluorescence. Frbm this solution it is precipitated i, Example 1 part by weight of di-p-chloro benzoyl I on cooling in small crystals. A particular purification is superfluous as the product obperylene dichloride satisfying the above contained is uncommonly pure. The same dye ditions is mixed with 6 parts byweight of powdered caustic potash and 20 parts by volume of quinoline and heated to boiling for about 40 minutes. The solution becomes beautifully violet blue. The dye stuff formed is separated after cooling by suction and then washed with alcohol and water. The output amounts to 0.65 parts by weight. The dye stuff is very pure and readily forms a vat of a blue color without any perceptible fluorescence. It dissolves in concentrated sulphuric acid with a blue tinged green color. Cotton is dyed blue with a violet tinge. The di-p-chloro benzoyl perylene dichloride is obtained by condensing 3,9 dichloro perylene with the chloro benzoyl chloride by means of aluminium chloride. The entire process is illustrated by the following formulae:

3,9-dichloro- 3,9-dichloro 4,10-di-p- Dyestufl perylene chlorobenzoylperylene f E wample IV.

1 part b weight of 3,9 dichloro perylene having a using point of 280 to 281 centigrade is mixed with 2% parts by weight of chloride of p-toluic acid, 3 parts by weight of powdered aluminium chloride and 40 parts by volume of bisulphide of carbon, and the mixture is left to itself for 24 hours, all moisture being excluded. The reaction mass of a deep bluish red color 'is then boiled for 3 hours, reflux being used whereby the reaction is completed, and further treated in the usual way above referred to. By recrystallizing from nitrobenzene the product is obtained, in

the form of orange colored needles melting at 325 centi'grade and dissolving in concentrated sulphuric acid with a deep violet tinged red colour.

mousse For converting the di-p-toluyl compound thus obtained, 1 part by weight thereof is boiled with 5 parts of powdered caustic potash -m 50 parts quinoline until the color changes. The dye stuff separated by cooling 1 part of 3,9 dichloro perylene and 1 parts of aluminium chloride are intimately mixed and suspended in 11 parts of bisulphide of carbon, and to the suspension 1.1

parts of chloride'of m-toluic acid are added, whereupon a violent reaction immediately begins, hydrochloric acid being evolved. The reaction mass becomes dee'ply blue. After the whole has been left to itself for 12 hours, it is heated in a water bath for 5 hours. After cooling, the double compound of aluminium chloride is first treated with ice and then with dilute hydrochloric acid and final- 1y, after the bisulphide of carbon has been distilled off, it is boiled with dilute hydrochloric acid. The raw product, the output of which is 1 parts, is dark brown in color, and melts after repeated recrystallization from "nitrobenzene at 334 centigrade. The compound is slightly soluble in solvents having a low boiling point. It is readily soluble in aniline and nitrobenzene. In concentrated 1 sulphuric acid it dissolves with a blue color. The di-m-toluyl' dichloro perylene thus obtained is the starting material for manufacturing a dye stufi' according to my invention.

1 part of the di-m-chloro toluyl dichloro perylene is heated to'boiling with parts of caustic potash in parts of quinohne. In a few minutes the color is changed into violet.

After the reaction is completed the whole is kept boiling for minutes. After cooling the liquid is drawn ofl by suction and the residue is washed with alcohol and water. On extracting the product so obtained with hot quinoline the dye stuff crystallizes on cooling from the solution. The compound is soluble in hot nitrobenzene, aniline and quinoline with a deep blue color and in concentrated sulphuric acid it dissolves with'a deep green color. Cotton is dyed violet.

The entire process is illustrated by the following formulae 3,9-dichloro4.10-di-mtoluylperylene Example VI.

The intermediateproduct is prepared by means of chloride of o:-:toluic acid as described in the immediately preceding example. The pure substance. is obtained from the raw product byrecrystallizing from nitrobenzene.

' 3,9-dichloroperylene It fuses at *':3i51 Centigrade and is only slightly soluble in solvents having a low'boiling point but is readily soluble in aniline and nitrobenzene. In concentrated sulphuric acid it dissolves with a blue color, the condensation toa dye stufi' being the same as described in Example V. The dye stuifdissolves in warm nitrobenzene, aniline, and

- thus obtained melts at 27 5 centigrade.

quinoline with a violetcolor and cotton is dyed with a considerably more marked blue tinge. v

The entire process is represented by the following formulae:

' CH: n o=f 1 o= toluylperylene Example VII.

1 part 3,9 dichloro perylene and 1.2 parts of a naphtoylchloride are caused to react in 3,9-dichlorw perylene -10'parts of bisulphide of carbon by means of 1 part of aluminium chloride. The mixture is left to itself for 12 hours and then it is heated for 3 hours in a water bath. The resulphuricacid it dissolves with a bluish green 7 color.

The closing of the ring for forming the dye stuff is brought about as follows 1 part 4-0: naphthoyl 3,9 dichloroperylene and 4 parts of caustic potash are heated in quinoline to boiling. After 10 minutes the reaction is completed and after cooling the dye stuff is separated by suction and is then washed'with alcohol and water. The crude dye stufi' dissolves in sulphuric acid with av greenish blue color and cotton is dyed blue. The entire process is illustrated by the following formulae:

l5 1 i i i 01 1 ,1 3,9dich1oro- 3,9dichloro 4 a-naphthoyl- Dyestufi perylene perylene What I claim is 1. A process for manufacturing dye stuffs of the isodibenzanthrone series consisting in 2 treating diaroyl dihalogen perylenes having two halogen groups in theperylene nucleus and each aroyl group occupying a position v peri to one of the halogen groups and having a free ortho position with alkali metal hydroxides at elevated temperatures in the presence of organic solvents.

nvoaess 2. A process for manufacturing dye stuffs of the isodibenzanthrone series consisting in treating diaroyldihalogen perylenes having two halogen groups in the perylene nucleus and each aroyl group occupying'a position peri to one of the halogen groups and having 1 a free ortho position with alkali metal hydroxides at elevated temperatures in the presence of aniline.

'3. A process for manufacturing dye stuffs of the isodibenzanthrone series consisting in treating dibenzoyl dibromo perylene having and each benzoyl group occupying a position peri. to one of the bromine atoms and having a free ortho position with alkali metal hydroxides at elevated temperatures in the' presenceof aniline.

In testimony whereof I have aflixed my signature.

ALOIS ZINKE. 

